Azo dyestuffs containing a benzthiazolyl group

ABSTRACT

AZO DYESTUFFS THAT ARE FREE FROM ACIDIC GROUPS IMPARTING SOLUBILITY IN WATER AND THAT CORRESPOND TO THE FORMULA   2-(B-N=N-),(D-N=N-)BENZOTHIAZOLE   IN WHICH D REPRESENTS A BENZENE RESIDUE THAT MAY BE SUBSTITUTED OF THE RESIDUE OF A COUPLING COMPONENT, AND B REPRESENTS THE RESIDUE OF A COUPLING COMPONENT FREE FROM ACIDIC GROUPS IMPARTING SOLUBILITY IN WATER.

United States Patent 3,707,532 AZO DYESTUFFS CONTAINING A BENZTHIAZOLYLGROUP Klaus Artz, Muttenz, and Visvanathan Ramanathan and Peter Moser,Basel, Switzerland, assiguors to Ciba- Geigy AG, Basel, Switzerland NoDrawing. Filed Dec. 23, 1969, Ser. No. 887,727 Claims priority,application Switzerland, Jan. 3, 1969, 11/69; June 11, 1969, 8,897/69Int. Cl. C09b 31/04 US. Cl. 260-458 3 Claims ABSTRACT OF THE DISCLOSUREAzo dyestuffs that are free from acidic groups imparting solubility inwater and that correspond to the formula in which D represents a benzeneresidue that may be substituted or the residue of a coupling component,and B represents the residue of a coupling component free from acidicgroups imparting solubility in water.

This invention provides new and valuable disazo dyestuffs that are freefrom acidic groups imparting solubility in water and that correspond tothe formula in which D represents a benzene residue that may besubstituted or the residue of a coupling component and B represents theresidue of a coupling component that is free from acidic groupsimparting solubility in water.

The preferred dyestuffs are those of the formula in which D has themeaning given above, d represents a hydrogen or a halogen atom, alow-molecular alkyl, alkoxy or mercapto group, an aryl, arylmercapto oraryloxy group or a cycloalkyl, cycloalkylmethyl or benzyl group, 0represents the same or an acylamino residue and R and R each representsa hydrogen atom or an alkyl residue that may be substituted.

Special mention may be made of the dyestuffs of the formulamonocarboxylic acid, the residue of an organic monosulphonic acid, forexample, methane-, ethaneor paratol uenemonosulphonic acid or theresidue of a carbamic acld ester or a carbonic acid monoester ormonamide, for example, phenoxycarbonyl, methoxycarbonyl andaminocarbonyl.

The groups R and R can be hydrogen atoms or low alkyl groups, that is tosay, alkyl groups containing 1 to 4, preferably 2 to 4, carbon atoms,for example, methyl, ethyl, n-propyl or n-butyl groups that can besubstituted 1n the usual manner, for example, benzyl or fl-phenethylgroups; halogenated alkyl groups, for example, fi-chloroethyl,B,;3,/i-trifiuoroethyl, fl -dichloropropyl or ;3-cyanoethyl groups;alkoxyalkyl groups, for example, B-ethoxyethyl or fi-methoxybutylgroups; hydroxyalkyl groups, for example, fi-hydroxyethyl or,8,'y-dihydroxypropyl groups; mtroalkyl groups, for example,B-nitroethyl groups; carbalkoxy groups, for example, B-carbo(methoxy-,ethoxyor propoxy)-ethyl groups (it being possible for the terminal alkylgroup to carry a cyano, cabalkoxy, acyloxy or amino group in w-position)or B- or -carbo(methoxyor ethoxy)-propyl groups; acylaminoalkyl groups,for example, fi-(acetylor formyl)-aminoethyl groups; acyloxyalkylgroups, for example, B-acetyloxyethyl or fL'y-diacetoxypropyl groups;B-(alkylor aryl)-sulphonylalkyl groups, for example,B-methanesulphonylethyl, B-ethanesulphonylethyl orB-(para-chlorobenzenesulphonyl)-ethyl groups; alkylorarylcarbamoyloxyalkyl groups, for example, B-methylcarbamyloxyethyl andfl-phenylcarbamyloxyethyl groups; alkoxycarbonyloxyalkyl groups, forexample, ,B(methoxy-, ethoxyor isopropyloxy)-carbonyloxyethyl,-acetamidopropyl, 18 (para nitrophenoxy)- ethyl,B-(para-hydroxyphenoxy)-ethyl, B-(fi'-acetylethoxycarbonyl)-ethyl,B-[(B'cyano-, hydroxy-, methoxyor acetoxy) ethoxycarbonyl] ethyl,cyanoalkoxyalkyl, flcarboxyethyl, fl-acetylethyL, 'y-aminopropyb,p-diethylaminoethyl-, fi-cyanoacetoxyethylandfi-bcnzoyl-fi-(paraalkoxyor phenoxy-benzoyl)-oxyethyl groups.

The groups R, and R generally contain not more than 18 carbon atoms.

The new dyestuffs may be obtained (1) by diazotizing anazobenzthiazolyl-Z-amine of the formula in which D represents theresidue of a substituted benzene or the residue of a coupling component,and then coupling it with a coupling component HB, or

(2) coupling an azobenzthiazolyl-Z-hydrazine of the formula oxidativelywith a coupling component HB, or (3) coupling anazobenzthiazolone-Z-hydrazone of the formula with a coupling componentto form a quaternated azo dyestutf, or

(4) diazotizing an acylaminobenzthiazolyl-Z-amine of the formula inwhich Ac represents an acyl residue, especially an acetyl residue,coupling the diazo compound with a coupling component HB, hydrolysingthe acylamino group situated on the benzene ring, diazotizing theprimary amino group and then coupling the resulting diazonium compoundwith a coupling component HD, and if desired or required, treating thedyestuflfs obtained,

if they contain quaternatable nitrogen atoms, with alkylating agents, itbeing essential that the reactants used in the reaction steps (1) to (5)be free from acidic substituents imparting solubility in water.

The G-phenylazobenzthiazolyl-Z-amines may be obtained in a manner knownper se in that a para-aminoazd benzene is thiocyan'ated inortho-position to the amino group and then condensed to formbenzthiazolyl-Z-amine. The para-aminoazobenzenes may be obtained, forexample, by coupling diazotized diazo components of the benzene serieswith aniline. Furthermore, 5- or 6-azobenzthiazolyl-Z-amines can also beobtained by selectively diazotizing 2,5- or 2,6-diaminobenzthiazole atthe 5- or 6-amino group with hydrochloric acid and an alkali metalnitrite and coupling with any desired coupling component. The 2-aminogroup on the 5- or 6-azobenzthiazolyl-2- amine can subsequently bediazotized with nitrosylsulphuric acid.

When coupling components are reacted with diazotizedZ-aminoacylaminobenzthiazoles, especiallyacetylaminobenzthiazole-Z-amines, for example, Z-amino-S- or -6-acetylaminobenzthiazole, the acyl group must subsequently be split olffrom the amino group, and the corresponding aminobenzthiazolyl-Z-azodyestuffs are obtained which are then diazotized and can be coupled withthe coupling components.

The preparation of Z-chlorothiazolylazo dyestuffs is described in Swisspatent specification No. 429,897. Amination of the 2-chlorine atom iseasily achieved by the action of ammonia in an organic solvent.

The following compounds are examples of suitable diazo components havinga benzthiazole residue:

o-Nm oar-ON: S

NEG =N HO OH which, by subsequent thiocyanation and a ring-closurereaction, lead to the diazo components of the formula can be derivedfrom the following diazo components D-NH aminobenzene,l-amino-4-chlorobenzene, 1-amino-4-bromobenzene,1-amino-4-methylbenzene, 1-amino-4-nitrobenzene, 1-amino-4-cyanobenzene,1-amino-2,5-dicyanobenzene, 1-amino-4-methylsulphonylbenzene,1-amino-4-carbalkoxybenzene, l-amino-4-cyanobenzene,1-amino-2,4-dichlorobenzene, 1-amino-2,4-dibromobenzene,1-amino-2-methyl-4-chlorobenzene,1-amino-2-trifluoromethyl-4'chlorobenzene,1-a'minc-2-cyano-4-chlorobenzene, 1-amino-2-carbomethoxy-4-nitrobenzene,1-amino-2-chloro-4-cyanobenzene, 1-amino-2-chloro-4-nitrobenzene,l-amino-2-br0mo-4-nitrobenzene, 1-amino-2-chloro-4-carbethoxy-benzene,1-amino-2-chloro-4-methylsulphonylbenzene,1-amino-2-methylsulphonyl-4-chlorobenzene,1-amino-2,4-dinitro-6-methylsulphonylbenzene,1-amino-2,4-dinitro-6-(2'-hydroxyethy1sulphonyl) benzene,1-amino-2,4-dinitro-6-(2'-chloroethylsulphonyl) benzene,1-amino-Z-methylsulphonyl-4-nitrobenzene,1-amino-2-methylsulphiny1-4-nitrobenzene, l-amino-2,4-dinitrobenzene,1-amino-2,4-dicyanobenzene, 1-amino-2-cyano-4-methylsulphonylbenzene,1-amino-2,6-dichloro-4-cyanobenzene,l-amino-2,6-dichloro-4-nitrobenzene,1-amino-2,4-dicyano-6-chlorobenzene, 4-aminobenzoicacid-cyclohexylester, 1-amino-2,4-dinitro-6-chlordbenzene and especially1-amino2-cyano-4-nitrobenzene;

also

1-aminobenzene-2-, 3- or 4-sulphonic acid amides,

for example,

N-methylor N,N-dimethylor diethylamide,

N,v-isopropyloxypropyl-2-aminonaphthalene-6-sulphonic acid amide,

N,' -isopropyloxypropyl-1-aminobenzene-2-, 3- or 4- sulphonic acidamide,

N-isopropyl-1-aminobenzene-2-, 3- or 4-sulphonic acid amide, N,'-methoxypropyl-1-aminobenzene-2-, 3- or 4-sulphon1c acid amide,N,N-bis(fi-hydroxyethyl)-1-aminobenzene-2-, 3- or 4- sulphonic acidamide, 1amino-4-chlorobenzene-Z-sulphonic acid amide,

and the N-substituted derivatives 2-, 3- or 4-aminophenylsulphamate,

2-amino-4, 5- or 6-methylsulphamate, Z-amino5methoxyphenylsulphamate,3-amino-6-chlorophenylsulphamate, 3-amino-2,6-dichlorophenylsulphamate,4-arnino-2- or 3methoxyphenylsulphamate,N,N-dimethyl-Z-aminophenylsulphamate,N,N-din-butyl-Z-aminophenylsulphamate,N,N-dimethyl-2-amino4-chlorophenylsulphamate,N,n-pr0pyl-3-aminophenylsulphamate,N,N-di-n-butyl-3aminophenylsulphamate,

O 3-aminophenyl N-morpholine-N-sulphonate,0(3-aminophenyl)N-piperidine-sulphonate,N-cyclohexyl-O-(3-arninopheny1)-sulphamate,N(N-methylaniline)O-(3-aminophenyl)sulphonate,N,N-diethyl-3amino-6-methylphenylsulphamate,N-ethyleneimine-O-(4-aminophenyl)-sulphonate,N,N-dimethyl-4-aminophenylsulphamate,

O- (n-propyl) O- 3-aminophenyl) sulphonate, 0,,8-chloroethyl-O-(2-aminophenyl) sulphonate, O-benzyl-O-(3-aminophenyl)sulphonate andO-ethyl-O- (4-amino-2,6-dimethylphenyl) sulphonate.

The following are examples of 4-aminoazobenzenes that can bethiocyanated and cyclized to form diazo components:

4-aminoazo-benzene, 3,2'-dimethyl-4-aminoazobenzene,2-methyl-Smethoxy-4-aminoazobenzene, 4-amin0-2-nitroazobenzene,2,5-dimethoxy-4-aminoazobenzene, 4-methoxy-4-aminoazobenzene,2-methyl4-methoxy-4-aminoazobenzene,3,6,4'-trimethoxy-4-aminoazobenzene, 4'-chloro-4-aminoazobenzene,

2'- or 3'chloro-4-aminoazobenzene,3-nitro-4-amin0-2,4'-dichloroazobenzene and4-aminoazobenzene-4-sulphonic acid amide.

Instead of the ionic diazo components free from groups impartingsolubility in water that are specified above, there may also be usedthose that contain fibre-reactive groups, for example, s-triazinylresidues carrying 1 or 2 chlorine or bromine atoms on the triazine ring,pyrimidyl residues carrying one or two chlorine atoms or one or twoarylsulphonyl or alkanesulphonyl groups on the pyrimidine ring, monoorbis-(' -halogeno-fl-hydroxypropy1)-amino groups,,8-halogeno-ethylsulphamyl residues, ,B-halogeno-ethoxy groups,B-halogeno-ethylmercapto groups, 2-chl0r0benzthiazolyl-fi-azo groups,2-chlorobenzthiazolyl-6-amino groups,'y-halogeno13-hydroxypropylsulphamyl residues, chloroacetylamino groups,u,;8-dibromopropionyl groups, vinylsulphonyl groups and 2,3-epoxypropylgroups.

The following are given as examples of suitable fibrereactive diazocomponents:

N,B-chloroethyl-3chloro-4-aminobenzene-sulphamide (hydrochloride),

N,fi-chlomethyl-4-aminobenzene-sulphamide (hydrochloride)3bromo4-amino-w-chloroacetophenone,

Nyy-chloro-p-hydroxypropyl-4-aminobenZene-sulphamide,

N,;3-chloroethyl-1-amino-4-naphthylsulphonamide,

N, fl-chloroethyl- 1-amino-3 ,5 dichlorobenzene-sulphamide and 4-('y-chloro[ihydroxypropoxy) aniline.

Coupling components of all kinds can be used in the manufacture of theazo dyestuffs, for example, those belonging to the benzene ornaphthalene series or to the series of heterocyclic coupling components.In addition to the phenols, for example, metaor para-cresol, resorcinoland 1hydroxy-3-cyanomethylbenzene, coupling components of the benzeneseries that may be specially mentioned are the aminobenzenes, forexample, aniline, 3-methylaniline, 2-methoxy-5-methylaniline,3-acetylamino-l-aminobenzene, N-methylaniline, N-B-hydroxyethylaniline,N ,8 methoxyethylaniline, N 8 cyanoethylaniline, N ,8chloroethylaniline, dimethylaniline, diethylaniline, N methyl N(benzylor B- phenylethyD-aniline, N-n-butyl-N-fl-chloroethylaniline, N-(methyl-, ethyl-, propylor butyl)-N-p-cyanoethylaniline,N-methyl-N-fi-hydroxyethylaniline, N-ethyl-N-B-chloroethylaniline,N-methyl-N-Bacetoxyethylaniline, N-ethyl- N-fl-methoxyethylaniline,N-B-cyanoethyl-N-fl-chloroethylaniline, N-cyanoethyl-N-(acetoxyorbenzoyloxyethyl) aniline, N,N-di-a-hydroxyethylaniline, N,N-di 3-acetoxyethylaniline, N-ethyl-N-Z-hydroxy-3chloropropylaniline,N,N-di-fl-cyanoethylaniline, N,N-di-B-cyanoethyl-3methylaniline,N-fi-cyan0ethy1-N- 8"-hydroxyethyl-3chloroaniline,N,N-di-,3-cyanoethyl-3-methoxyaniline,N,N-dimethyl-3-acetylaminoaniline,N-ethyl-N-B-cyanoethyl-3acetylaminoaniline, N,N-di-ficyanoethyl-2methoxy-S-acetylaminoaniline, N-methyl-N-phenacylaniline,N-B-cyanoethyl-2-chloronaniline, N,N-diethyl-3trifluoromethylaniline,N-ethyl-N-phenylaniline, diphenylamine, N-methyldiphenylamine,N-methyl-4-ethoxydiphenylamine or N-phenylmorpholine, and also, forexample, amines of the formula NHOOR' in which R, represents a hydrogenatom or an 'alkyl or alkoxy group, R' represents a cyanoalkoxyalkylgroup, R';, represents a hydrogen atom, a cyanoalkoxyalkyl group or anacyloxyalkyl group and RC; represents a hydrogen atom, an alkyl,cycloalkyl or alkoxy group that may be substituted or a benzene residue,and especially those of the formula /CH2CHzOCH2CHzCN N in which R and Rhave the meanings given above.

Valuable results may also be obtained with coupling components of theformulae and ONE-OIIzCHa-O-CIEDCILCN in which R' has the meaning givenabove, X represents an acylamino group and alkyl" represents, forexample, a methyl, ethyl or propyl group.

The following coupling components are given as examples:

(?CH3 qomomocmomom:

C2H5 Qmcnmmocnwmcnn NHCHO OCH:

CH OH OCHzCHzCN (311201120 0 O CH; nnco CH:

NHCHzCHaOCHzCHzCN NH0 0 OH! OCH;

NHCHZCHZO CO CH;

NHCOCH;

NHCHzCHzOCHzCHzCN NBC 0 O 02H:

OCH.

NHCO CH2CH3 The following are mentioned as examples of couplingcomponents of the naphthalene series, especially naphthols andaminonaphthalenes:

Heterocyclic coupling components are, for example, indoles having acidhydrogen atoms, for example, 2-methylindole, 2,5 dimethylindole, 2,4dimethyl 7 methoxyindole, 2-phenylor 2 methyl 5 ethoxyindole, NJ?-cyanoethyl 2 methylindole, 2-methy1-5- or -6-chloroindole,1,2-dimethylindole, l methyl 2 phenylindole, 2 methyl 5 nitroindole, 2methyl 5 cyanoindole, 2 methyl 7 chloroindole, 2 methyl 5 fluoroor-5-bromoindole, 2 methyl 5,7 dichloroindole' or 2- phenylindole and 1cyanoethyl 2,6 dimethylindole. The indole may be further described assubstituted indole wherein the substituent is selected from the groupconsisting of methyl, phenyl methoxy, ethoxy, fl-cyanoethyl, chloro,nitro, cyano, fluoro and bromo; pyridines, for example, 3 cyano 2,6dihydroxy 4 methylpyridine; pyrazoles, for example, 1 phenyl 5aminopyrazole or 3 methylpyrazolone 5 or 1 phenyl 3- methylpyrazolone 5,1,3 dimethylpyrazolone 5, 1- butyl 3 methylpyrazolone 5, 1 hydroxyethyl3- methylpyrazolone-S, l cyanoethyl 3 methylpyrazolone-5, 1 (orthochlorophenyl) 3 methylpyrazolone-5 and 3 carbomethoxypyrazolone 5. Thepyrazolones may be further described as substituted pyrazolones whereinthe substituent is selected from the group consisting of phenyl, Calkyl, hydroxyethyl, cyanoethyl, chlorophenyl and carbomethoxy;quinolines, for example, 8 hydroxyquinoline, l methyl 4 hydroxyquinoline2 and N ethyl 3 hydroxy 7 methyl l,2,3,4 tetrahydroquinone orpyrimidines, for example, barbituric acid, and also 1,3-indandione,1,8-naphthindandione, dimedone, acetoacetic acid anilide,meta-hydroxy-N,N-diethylaniline, 3-hydroxy-4'-methyldiphenylamine,hydroquinone-monomethyl ether, acetylacetone, 5 hydroxybenzthiazole and1,2 diphenylpyrazolidine 3,5 dione, and, finally, coupling components ofthe aniline series, for example, 1,2,3,4 tetrahydroquinolines (known astetrahydroquonolines) and benzomorpholines, for example,tetrahydroquinoline, N,}3-cyanoethylor N fl hydroxyethyltetrahydroquinoline, N 7 ,7 dihydroxypropyltetrahydroquinoline, N [3,dihydroxypropyl 7 methoxy tetrahydroquinoline, N [3, dihydroxypropyl- 5acetylamino tetrahydroquinoline, N fl hydroxyethyl 2,2,4 trimethyltetrahydroquinoline, N-B-hydroxyethylbenzomorpholine and N findihydroxypropyl-S-acetylaminobenzomorpholine.

Further coupling components of the aniline series that may be mentionedare those containing a quaternatable or quaternated group, for example,N-methyl-N,2-dimethylaminoethylaniline, N,2-(N-ethyl N phenyl)-aminoethylpyridinium chloride and also, for example, compounds of theformulae NHCOCHa Diazotizable amines can also be mentioned as couplingcomponents of the aniline series, fore example, l-amino-3-methylbenzene, 1 amino 2 methoxy 5 methylbenzene, l-aminonaphthalene,and so forth; when used, aminoazo dyestuifs are formed that can bediazotized and then coupled with the coupling components specified aboveto form disazo or polyazo dyestuffs.

Finally, there may also be mentioned coupling components having acidhydrogen atoms, for example, malodinitrile, phenylsulphonylacetonitrile,cyanoacetic acid methyl ester, cyanoacetic acid ethyl ester, cyanoaceticacid butyl ester, 4,5-dimethyland 4,5-diphenyl-imidazole.

Diazotization of the diazo components specified can be carried out, forexample, with a mineral acid and sodium nitrite or, for example, with asolution of nitrosylsulphuric acid in concentrated sulphuric acid,according to the position of the amino group concerned.

Coupling can also be carried by a method known per se, for example, in aneutral to acid medium, if necessary, in the presence of sodium acetateor a similar buffer that influences the rate of coupling, or a catalyst,for example, dimethylformarnide, pyridine or a salt thereof.

Coupling may also be effected with advantage by combining the componentsin a mixing nozzle. By this is meant a device in which the liquids to bemixed are combined in a comparatively small space, at least one of theliquids being conducted through a nozzle, preferably under pressure. Themixing nozzle can be constructed on the principle of a water-jet pump,and function in like manner, the delivery of one of the liquids in themixing nozzle corresponding to the delivery of water in a waterjet pump,and the delivery of the other liquid into the mixing nozzlecorresponding to the compound in the container of the water-jet pump tobe evacuated. The latter delivery of liquid can also be effected underpressure. However, other devices can also be used to effect speedy and,optionally, continuous mixing in a small space.

The term coupling as used herein also includes the so-called oxidativecoupling in which the diazonium compound of the diazo component isreplaced by a corresponding hydrazine or hydrazone. By the process ofoxidative coupling it is possible to obtain the quaternated compounds inone step, in this case, the benzthiazolium compounds.

The following model of a monoazo dyestuff illustrates how coupling andsimultaneous quaternation take place:

\ -GK +tH.

Suitable dehydrogenating or oxidizing agents are, for example,atmospheric oxygen, hydrogen peroxide, hypochlorites, persulphates,perborates, iron(III) salts, copper (III) salts, mercury(II) salts,lead(IV) salts and cerium (IV) salts and hexacyanoferratesflll); ifnecessary, oxygen carries may also be used concomitantly, for example,heavy metals and the salts thereof.

The hydrazones can be prepared according to known methods [R.Riemschneider and S. Georgi, Monatshelfte fiir Chemie, Vol. 91, 623(1960); S. Hiinig et al., Angewandte Chemie, vol. 70, 215 (1958); vol.74, 818 (1962); vol. 80, 343 (1968); Chimia, vol. 15, 133 (1961); H.Baumann and H. Dehnert, Chimia, vol. 15, 163 (1961)].

The dyestufis can be quaternated by virtue of the nitrogen atom in thebenzthiazole ring and/or if the residues D and/ or B containquaternatable nitrogen atoms, quaternation preferably being carried outas the last step.

Quaternatable dyestufls of the kind mentioned correspond, for example,to the General Formula 1 and fall into the following categories:

(1) only the benzthiazole residue is quaternatable,

(2) the residue D or the residue B is quaternatable in addition to thebenzthiazole residue,

(3) the two residues D and B are quaternata'ble in addition to thebenzthiazole residue. The residues B and/or 10 D in this case maycorrespond to the following formulae:

The residue D can also correspond to the formula in which D represents aphenylene residue that may be substituted.

Dyestuffs that are specially preferred are those corresponding to theformulae in which Y and Y each represents a pyridium or trialkylammoniumgroup, for example, a dimethylbenzylammonium group.

Quaternation is effected by a treatment with esters of strong mineralacids or organic sulphonic acids, for example, dimethyl sulphate anddiethyl sulphate, alkylhalides, for example, methyl chloride, methylbromide or methyl iodide, aral kylhalides, for example, benzyl chloride,esters of low-molecular-weight alkane-sulphonic acids, for example, themethyl ester of methane-, ethaneor bntane-sulphonic acid and the alkylesters of (4- methyl-, 4-chloroor 3- or 4-nitro)benzenesulphonic acidwhich form as anions halogen, sulphuric acid semi-ester, alkane orbenzenesulphonic acid anions, preferably with heating in an inertorganic solvent, for example, xylene, carbon tetrachloride,ortho-dichlorobenzene or nitrobenzene. However, other solvents may alsobe used, for example, acetic anhydride, dimethylformamide, acetonitrileor dimethyl sulphoxide. The quaternated dyestuffs preferably contain asanion Y- the residue of a strong acid, for example, the residue ofsulphuric acid or semi-esters thereof, or a halide ion; however, theycan also be used as double salts, for example, with zinc chloride, or asfree bases.

The new water-insoluble dyestuffs, mixtures thereof and mixtures ofthese dyestuffs with other azo dyestuffs are eminently suitable fordyeing and printing leather, wool, silk and, in particular, syntheticfibres, for example, acrylic and acrylonitrile fibres, polyacrylonitrilefibres and copolymers of acrylonitrile and other vinyl compounds, forexample, acrylic esters, acrylic amides, vinylpyridine, vinyl chlorideor vinylidene chloride, copolymers of dicyanoethylene and vinyl acetateand of acrylonitrile block copolymers, fibres made of polyurethanes,unmodified polyolefins, polyolefins modified with metals, for example,aluminium, cobalt, copper, vanadium, chromium, zinc and, in particular,nickel, or basified polyolefins, for example, polypropylene, cellulosetriacetate and secondary acetate, and, in particular, fibres made ofpolyamides, for example, nylon 6, nylon 6.6 or nylon 12, and of aromaticpolyesters, for example polyesters made from terephthalic acid andethylene glycol or 1,4-dimethylcyclohexane, and copolymers ofterephthalic and isophthalic acid and ethylene glycol.

' This invention therefore also relates to a process for dyeing orprinting textile materials based on synthetic fibres, especiallypolyester fibres, or, when the dyestuffs are quaternated, acrylicfibres, wherein there are used dyestuffs of the formula that are freefrom groups imparting solubility in water, in which formula D representsa benzene residue that may be substituted or the residue of a couplingcomponent and B represents the residue of a coupling component that isfree from acidic groups imparting solubility in water.

When dyeing is carried out in an aqueous liquor, the water-insolubledyestuffs are advantageously used in a finely divided form and dyeing iscarried out in the presence of a dispersing agent, for example, sulphitecellulose waste liquor, or a synthetic detergent, or a combination ofdifferent wetting and dispersing agents. Prior to dyeing, it isgenerally advantageous to convert the dyestuff into a dyeing preparationthat contains a dispersing agent and the finely divided dyestuff in aform such that a fine dispersion is formed when the preparation isdiluted with water. Such dyestuff preparations may be obtained in knownmanner, for example, by grinding the dyestuff in a highly efficientgrinding device in the dry or wet state in the presence or absence of adispersing agent.

To obtain stronger dyeings on polyethylene terephthalate fibres it isadvantageous to add a swelling agent to the dyebath, or to carry out thedyeing process under superatmospheric pressure at a temperature of aboveC., for example, at C. Suitable swelling agents are aromatic carboxylicacids, for example, salicylic acid, phenols, for example, orthoorpara-hydroxydiphenyl, aromatic halogenated compounds, for example,ortho-dichlorobenzene or diphenyl.

To fix the dyestuff, the padded polyester fabric is heated to atemperature above 100" C., for example, to a temperature between and 210C., preferably after drying, for example, in a current of warm air.

The dyeings obtained in accordance with this process can be subjected toan aftertreatment, for example, by heating with an aqueous solution of anon-ionic detergent.

The dyestuffs may also be applied by printing processes. In this methodof application a printing paste, for example, is used which contains thefinely divided dyestuff as well as the adjuvants normally used inprinting, for example, wetting and thickening agents.

The process yields strong dyeings and prints possessing good propertiesof fastness.

The dyestuffs of the invention are also specially suitable for dyeingand printing polypropylene fibers modified with nickel, the dyestuffsused preferably being those that contain, in ortho-position to the azogroup, groups of atoms capable of forming complexes, for example,hydroxy, carboxyl, carbalkoxy and alkoxy groups.

Dyestuffs that are specially suitable for dyeing polypropylene modifiedwith nickel are those of the formula in which D has the meaning givenabove and B represents a coupling component containing in ortho-positionto the azo group a group capable of forming a complex.

The new water-insoluble dyestuffs can also be used in thespin-coloration of polyamides, polyesters and polyolefins. The polymerto be coloured is advantageously mixed with the dyestuff in the form ofa powder, grains or chips, in the form of a solution ready for spinningor in the form of a melt, the dyestuif being in the dry state or in theform of a dispersion or solution in a solvent that may be volatile.After the dyestuff has been homogeneously dispersed in the polymersolution or melt, the mixture is processed in known manner into fibres,yarns, monofilaments, films and so forth by casting, moulding orextruding.

The new water-insoluble quaternated dyestuffs or dyestulf salts aresuitable for dyeing and printing a very wide variety of syntheticfibres, for example, polyvinyl chloride, polyamide, polyurethane andespecially polyacrylic fibres.

The following examples illustrate the invention, the parts andpercentages being by weight, unless otherwise stated.

EXAMPLE 1 2.54 parts of 2-amino-6-phenylazobenzthiazole are dissolved at50 C. in 30 parts of 85% phosphoric acid, the solution is cooled to -10C. to l5 C, and then 0.69 part of sodium nitrite is strewn in. The batchis stirred for 3 hours at -10 C., the diazonium compound is run at 0 C.into a prepared solution of 2.43 parts of N-cyanoethoxyethyl-N-cyanoethylaniline (dissolved in 50 ZOEG m m 3 E|NHHUII Em 0 z ofi o M M 8 a 45 m ofiuol E5 "MO 0 OQZ m 025 mu 2am mm E.5 zo m o ofi o o n l l H1O mo/ \ZI. 0 m0 0 O "N0 "MO m0 m 25 2 05am mmdo w N Z I m moooo m o moooofi o 0 woo 8 63m SHOOHQO ZO N O m m 25% 308mm 4 2' "m0 .Uwm .ZOHWNOOJHNO ZUWQOI HUI m nmo ew O O Z 63w Z HQO m 0m M 00m m 95% 3 95m 2 m Z "0 Em mo 50 mofiooomz moo 5205 QH OOOOHQO 000OJN O m0 O I 625a mm 35m 3 m 2' 3m mo 056 E0 ofi o m 3 mm m 5H N Q 19 a20 (dissolved in 130 parts of methanol) and the batch is 80% acetic acidand 2 parts of a 5% aqueous dispersion stirred for 1 hour at C. 250parts of ice are then added, of the compound obtained in accordancewith'Example 3 the batch is stirred for a further 60 minutes, thedyestuff in 400 parts by volume of Water and having a pH of 4 to thatprecipitates is isolated by filtration and then washed 5. The bath isheated to boiling temperature in the course until free from acid. Thedyestuif of the formula 5 of 45 minutes and dyeing is carried out for 30minutes NH0 0 (DH-CH:

Br r

is obtained in a good yield. It dyes polyester fibers, at the boil. ThepH is then adjusted to 12 by the addition cellulose acetate fibres andpolyamide fibres a bluish red of sodium carbonate and boiling iscontinued for a shade possessing good properties of fastness. further 30minutes. The textile material is then well rinsed The 2 amino 6(4-nitrophenylazo)-benzthiazole With water and dried. A brilliant bluishred dyeing conspecified above is obtained by thiocyanation of 4-amino-2O taining a high proportion of non-extractable dyestutf is4'-nitroazo-benzene with ammonium thiocyanate in glacial tain daceticacid and subsequent cyclization by the action of T e dyestuff dispersionused is obtained by grinding bromine to form the b thi l parts ofdyestufi with 140 parts of Water and 40 parts of The dyestuffs li t d inthe following table f th the sodium salt ofdinaphthylmethane-disulphonic acid. formula X EXAMPLE 4 R i I 4.08 partsof 2-amino-6-(4'-N-cyanoethyl-N-acetoxyethylaminophenylazo)-benzthiazole(prepared :by mono- R2 diazotization of 2,6-diaminobenzthiazole indilute hydro- Y chloric acid and coupling with N-cyanoethyl-N-ethoxyarcobtaincd y diazotizaticn and p g in accordance ethylaniline) aredissolved at 50 0. in 30 parts of 85% with the procedure described inthis example. The shades phosphoric acid, the solution is cooled to 10to -15 indicated in the last column are obtainable on polyester C. andthen 0.69 part of sodium nitrite is strewn in. The fibres, celluloseacetate fibres and polyamide fibres by batch is stirred for 3 hours at-l0 C., the diazonium both dyeing and pnntmg. compound is run at 0 C.into a prepared solution of TABLE III 1 X Y R; R2 Shade 1.-.. N -H-NHCOOH2C1 --CzH4OCOCHa C2H4OCOCH3 Violet.

2 Same as above- --H 01 -C2H4CN C2HON Bluish red.

N NH N OCH;

3.-.; N H NHCOCH=CH(|7HCH1 4311140000113 4321140000113 Violet.

H F3 CF2 C 4.... Same as above. H 01 -C2H4OCH3 --C:HCH; D0.

awn-( N t CzHrOzHb 6...- Same as above. H -H -CzHr CH; Red.

G2H4N/ Example of dyeing procedure 1.74 parts ofl-phenyl-3-methyl-5-pyrazolone (dissolved in 200 parts of alcohol) andthe batch is stirred for 1 10 parts of a knitted nylon 6.6 fabric(Helanca) ar hour at 0 C. 250 parts of ice are then added, the batchentered at 30 C. into a dyebath containing 0.2 part of 75 is stirred fora further minutes, the dyestuff that pre- 21 22 cipitates is isolated byfiltration and then washed until is obtained in a good yield. It dyespolyester fibres, cellufree from acid. The dyestuff of the formula loseacetate fibres and synthetic polyamide fibres a scarlet shade possessinggood properties of fastness.

-N CNH-iCZ t t? s HO-C N CH 0001! C is obtained in a good yield. It dyespolyester fibres, cellu- EXAMPLE 7 lose acetate fibres and polyamidefibres a scarlet shade possessing good properties of fastness. 20.7parts of Z-amino-6-acetylaminobenzthiazole are diabotized in a mixtureof formic acid and concentrated EXAMPLE 5 sulphuric acid with sodiumnitrite. The diazonium salt 3.2 parts of2-amino-6-(2'-hydroxynaphthylazo)benzthat is formed thereby is coupledwith 16.5 parts of N- thiazole (prepared by monodiazotization of2,6-diaminoethyl-N-ethoxyaniline dissolved in glacial acetic acid.

benzthiazole in dilute hydrochloric acid and coupling Working upproduces 26.5 parts of Z-(para-N-ethyl-N- with B-naphthol) are dissolvedat 50 C. in 30 parts ofethoxyamino)phenylazo-6-acetylarninobenzthiazole.

85% phosphoric acid, the solution is cooled to 10 to 19.2 parts of thiscompound together with 1,000 parts l5 C., and then 0.69 part of sodiumnitrite is strewn of 2 N sulphuric acid are refluxed for one hour, thesoluin. The batch is stirred for 3 hours at 10 C., the tion obtained isvacuum filtered, and the pH of the diazonium compound is run at 0 C.into a prepared solufiltrate is adjusted to 4 to 5 with concentratedsodium tion of 2.43 parts of N-cyanoethoxyethyl-N-cyanoethylhydroxidesolution while cooling. The compound that preaniline (dissolved in 50parts of alcohol) and the batch is cipitates thereby is isolated byfiltration, Washed with stirred for 1 hour at 0 C. 250 parts of ice areadded, the water and dried. 10.0 parts of 6-amino-2-(para-N-ethylbatchis stirred for a further 60 minutes, the dyestutfN-ethoxyaminophenylazo)benzthiazole are obtained. that precipitates isisolated by filtration and washed until 3.4 parts of this compound arediazotized in a manner free from acid. The dyestuif of the formula knownper se with sodium nitrite in dilute hydrochloric is obtained in a goodyield. It dies polyester fibres, celluacid, and the diazonium salt thusformed is coupled with lose acetate fibres and synthetic polyamidefibres a red 1.65 parts of N-ethyl-N-ethoxyaniline in hydrochloric shadepossessing good properties of fastness. acid solution. The addition ofsodium acetate to establish a pH of 4 to 5 brings about the isolation of4.3 parts of EXAMPLE 6 2,6 bis-(:para-N-ethyl-N-ethoxyaminophenylazo)-benz Parts of Y Y thiazole, adyestufi' that dyes polyester fibres a reddish thiaz (pr p ymonodiaZOtiZatiOH 0f brown shade possessing good general properties offastbeHZlihiflZOle in dilute y acid and p g with ness when appliedaccording the high-temperature process. Z-methylindole) are dissolved atC. in 30 parts of 2.6 parts of 2,6 bis (para- N-ethyl-N-ethoxyaminophosphoric acid, the SOlIltiOn is cooled to 10 t0phenylazo)-benzthiazole are quaternated with dimethyl --15 C., and then0.69 part Of Sodium nitri e i str n sulphate in dimethyl-formamide at atemperature .of in. The batch is stirred for 3 hours at -10 C., the 50to C. After quaternation, the course of which is diazonium compound isrun at 0 C. into a prepared solufollowed by thin-layer chromatography,the solvent is dis ti of 2,43 parts ofN-cyanoethoxyethyl-N-cyanoethyltilled under reduced pressure, theresidue is dissolved in aniline (dissolved in 50 parts of alcohol) andthe batch hot water, and the dyestuif salt is precipitated from the isstirred for 1 hour at 0 C. 250 parts of me are then filtered solution bythe addition of sodium chloride and added, the batch is stirred for afurther 60 minutes, the 55 ZnCl The dyestuff of the formula dyestutfthat precipitates is isolated by filtration and dyes polyacrylonitrilefibres a reddish blue shade possesswashed until free from acid. Thedyestufl? of the formula ing good properties of fastness.

The following table shows a number of dyestuffs prepared in an analogousmanner and indicates the shades they produce on polyacrylonitrilefibres.

- otnioN s olrnoczmoN CN=NB TABLE IV D B Shade 1 CzHs CZHAOH Reddishblue.

2 Same as above Do.

3 C3115 -d0 Blue.

4 01H; DO.

?H: N CH;l ICHzHC-C CH: OCOCHa EXAMPLE 8 acid, and the diazonium saltthat is formed thereby is evaporated to dryness and the powdery residueis pasted 40 with water, vacuum filtered, the filter residue is washedCH2CH7 with water until the washings run neutral and then dried. 9.4parts of 6 amino-2-(para-N-morpholinophenylazo)- benzthiazole areobtained.

3.4 parts of this compound are diazotized in a manner known per se withsodium nitrite in dilute hydrochloric coupled with 1.65 parts ofN-phenylmorpholine in hydrochloric acid solution. The addition of sodiumacetate to establish a pH of 4 to 5 elfects the isolation of 2,6-bis-(para-N-morpholinophenylazo)-benzthiazole, a dyestulf that dyespolyester fibres a reddish brown shade.

2.6 parts of 2,6-bis(para N morpholinophenylazo)- benzthiazole arequaternated with dimethyl sulphate in dimethylformamide at a temperatureof to C. After quaternation, the course of which can be followed bythin-layer chromatography, the solution is distilled under negativepressure and the residue is dissolved in hot water; the dyestulf salt isprecipitated from the filtered solution by the addition of NaCl and ZnClThe dyestufi of the formula CHzCHz S CHzCHg C-N=N-B TABLE V D B Shade 1HO (12H; Reddlsh blue.

H O CzH4 2.-'..---- HO Cg Same 85 above....-.' DO.

H O 02H;

3 C) C -i 4 02H; 02H: D0.

N N C2H5 CIHE EXAMPLE 9 CHz-CH-CHz-N-CH:

40 CH3-0 H3 in 100 parts of 2 N hydrochloric acid, and the batch isstirred for 1 hour at 0 C. 250 parts of ice are then added, the batch isstirred for a further minutes, the pH is 5 adjusted to 4 with sodiumacetate, and the dyestufi of the formula CH CH:

is cooled to room temperature, and the pH is adjusted to is precipitatedby the addition of NaCl and ZnCl It is 5 by the addition of sodiumcarbonate. The precipitate is isolated by vacuum filtration, washed withwater and dried. 15.5 parts of 2-amino-6-(para-chlorophenylazo)-benzthiazole are obtained.

5.8 parts of this compound are dissolved at 50 to C. in 10 parts ofphosphoric acid, the solution is cooled to l0 to 15 C., and then 1.38parts of sodium nitrite are added. The batch is stirred for 3 hours at--10 C. and the diazonium salt solution is then run at 0 C. into aprepared solution of 7.8 parts of then isolated by vacuum filtration anddried.

The dyestufi so obtained is reacted with dimethyl sulphate indimethylformamide at a temperature of to C. After the reaction, thesolvent is removed by dis- 60 tillation, the residue is dissolved in hotwater, the batch is filtered and the dyestuif salt is precipitated withNaCl and ZnCl The dyestuif so obtained of the formula 75 duce onpolyacrylonitrile fibres.

CH3 1+ DN=N C--N=NB TABLE VI D B Shade 1 03115 Blue.

CHzCHaN 2 Same as above 11 D0.

CHaCHaI?I-OH3 3 CnHs Bluish green.

OzN

oH,cHoH,1-icH,

OHaO C CH3 4 Same as above (lJ H Do.

I CHzCH -N 6 CzHs D0.

CHlCECHflI$-CH3 (31130 C O CH:

6 Same as above -4 (3111 Do.

CH2CH2'N 7 C51: (llzHs Greenish blue.

C 00,114 CHaGHCH -lf-CH;

CHaO C CH3 8 Same as above (lhHr Do.

CH2C zN 9 /CH:Cgg $1115 DO.

0 N -N CH: l

CHlCH] CHzCHCHz-IIICH:

CHaO C 0 CH3 10 (IHHAOH Blue.

11 Same as above Bluish green.

12 .do Do.

13 01H: ---..d0 Roddish blue.

H O C1114 EXAMPLE 10 8.5 parts of2-amino-6-(2'-methyl)-phenylazo-4-methylbenzthiazole are dissolved in 75parts by volume of 85% phosphoric acid, the solution is cooled to -10 to15 C. and then 2.27 parts of sodium nitrite are strewn in. The batch isstirred for 3 hours at 10 to 15 C.,

2.27 parts of urea are added and stirring is continued for 15 minutes.The diazonium compound so obtained is run at 0 C. into a solution of4.32 parts of fl-naphthol in 225 parts by volume of alcohol and at thesame time a 15% sodium hydroxide solution is added dropwise to keep thepH of the coupling mixture at 7 to 8. The mixture is stirred for 2 hoursat C., diluted with cold water, and the dyestuiI' that precipitates isisolated by filtration and washed until free from salt. The dyestutf soobtained, which corresponds to the formula TABLE VII 1 II III 1 CH;l-phenyl-S-methyl-fi-pyrazolone Orange.

N CH: C-CHR S 2. Sameas abov S-dimethylaminophenol. Reddish violet. a; 1Dimpdrmn Orange. 4 do Para-creed! Green.

5 N 5,6,7,8-tetrallydro-2-naphthol Olive.

C-OH:

6 Same as abov 3-diethylnminophenol.-.;--..; Reddish violet. 7 do2,4'dimethylphenoluu Green. 8 do Malonie acid dinitrile Yellow. 0 doIndoxyl Orange. 10 do 1,3-dimethyl-5-pyrazolone Do.

11 N 3-11ydroxy-4-methyldiphenylamine Violet.

CH3 H3O C-NH:

. Same as above Hydroquinonemonomethylether Olive.

do l-phenyl-2-methylpyrazolidine-B', Golden yellow. dol-methyli-hydroxy-2-quinoline Brown.

N Aeetylaeetone Scarlet.

0"NHQ 16 Same as abov fi-chloro-l-naphthoL. Grey. 17 do B-NqphthnlReddish black.

18 N 1-butyl-3-methyl-5-pyrazolone Orange.

C-NH2 19 Same as above Q-phenylnaphthylamine Olive. 20 --d04-cyelohexylphenol Green.

21 N 3-ethylaminophenol Violet.

C-NH:

22 Same as above 4,5-diphenylimidazo1e 23 dol-meta-toluyl-3-methyl-5-pyrazo1o 24 OH: 5,8-dichloro-l-naphthol Grey.

ONH: I S CH3 25 Sameasabove 1,3-indanedione Scarlet. 26 do4,5-dianisylimidazole Do.

TABLE VII-Continued I II III 27 N 4-ethoxy-1-naphthol Black.

CNH2

28 Same as above 4-isopropylpheno1 Green. 2 do-. Acetylacetone Scarlet..do..- 4-hydr0xycoumarin- Orange.

31 N l-butyl--hydroxy-Z-quinoline Brown;

CNH2

32 Same as above l-isopropyl-Zi-rnethyl-E-pyrazolone---. Orange. 33.do.. 1,2-diphenylpyrazolidineBj-dione Golden yellow.

34 N Acetoacetie acid anilide Orange.

C-NH:

35... Same as above 3 -do- 37 (10,-

38 O(|JH; 1,3-indanedione- Scarlet;

CNH: \S

39 Sameasabove 5.6,7,8-tetraphydro-Z-naphthol Olive. 40 .-dol-phenyLB-methyl-fi-pyrazolone Orange.

41 N s-chloro-l-naphthol Grey.

CNH:

C4Hn

42 Same as absve-.;. ...r.;.;.;.;..-;.--;1-(4'-chlorophenyl)-3-methyl5-pyrazolone-.t Orange; 43 do- Para-cresolGreen.

Printing procedure 1 part of the dyestufif obtained in the mannerdescribed in Example and 1 part of 1,1'-dinaphthylmethane-2,2'-disulphonic acid are ground in a ball mill to form a fine aqueous pastehaving a dyestuif content of 10%. A mixture is then prepared from thefollowing components using a high-speed stirrer:

100 parts of the paste described in the preceding paragraph 310 parts ofcold water 50 parts of urea 500 parts of a 5% aqueous sodium alginatethickening parts of ammonium sulphate obtained.

EXAMPLE 11 20.7 parts of 2-amino-6-acetylaminobenzthiazole arediazotized with sodium nitrite in a mitxure of formic acid andconcentrated sulphuric acid. The diazonium salt is coupled with 20.6parts of N-ethyl-N-y-dimethylaminopropylaniline dissolved in dilutehydrochloric acid. Working up yields 35.0 parts of2-(para-N-ethyl-N-y-dimethylaminopropylaminophenylazo-6-acetylaminobenzthiazole.

21 parts of this compound and 1,000 parts of 2 N sulphuric acid arerefluxed for one hour, the solution so obtained is vacuum filtered, andthe pH of the filtrate is adjusted to 4 to 5 with concentrated sodiumhydroxide solution while cooling. The compound that precipitates therebyis isolated by filtration, washed with water and dried. 15.0 parts of6-amino-2-(para-N-y-dimethylaminopropylaminophenylazo)-benzthiazole areobtained.

3.8 parts of this compound are diazotized in known manner with sodiumnitrite in dilute hydrochloric acid and the diazonium salt so obtainedis coupled with 2.05 parts of N-ethyl-N-'y-dimethylaminopropylaniline inhydrochloric acid solution. The pH is adjusted to 4 to 5 with sodiumacetate to isolate 5.1 parts of 2,6-bis-(para-N- ethyl N'y-dimethylaminopropylaminophenylazo)-benzthiazole.

3.0 parts of2,6-bis-(para-N-ethyl-N-y-dimethylaminopropylaminophenylazo)-benzthiazoleare quaternated with dimethyl sulphate in dimethylformamide at atemperature of to C. After quaternation, the course of which is followedby thin-layer chromatography, the solvent is distilled under negativepressure, the residue is dissolved in hot water, and the dyestulf saltis precipitated from the 33 34 filtered solution by the addition of NaCland ZnCl Th cresol, resorcinol, 1-hydroxy-3-cyanomethyl-benzene,adyestulf, which corresponds to the formula naphthol, fl-naphthol,4-methoxy-l-hydroxynaphthalene,

(lJzHs (3H3 CHs-N-OHzCHzHz O $5 m a S H CH CH N-CH H: 2 2 2- I dyespolyacrylonitrile fibres a blue shade. 2 hydroxy8-methyl-sulphonylaminonaphthalene, 2-hy- The following table shows anumber of dyestuffs that droxynaphthalene-3-carboxylic acid anilide,2-hydroXy-8- can be prepared in an analogous manner. The shades theyacetylaminonaphthalene, l-hydroxynaphthalene 3 sulproduce onpolyacrylonitrile fibres are also indicated. phone methylene ether-4,2-hydroxynaphthalene-6-sul- %N=N-=-A 5/ TABLE VIII D A Shade 1 CQA (lzHu B1118. r w-Q G r Curie-01120112011, crnoH,oH,-r3-om CH: CH: 1 CH3CH3 2 Cg} (3 13, D0. 5 l E CH -iW-CHzCH CH, omomom-n-orn 0 o H; 0 OH: 1CH: CH;

We claim: phonamide, Z-hydroxynaphthalene-6-sulphonic acid di- 1. Adyestuflfs that are free from acidic groups immethylamide,1-hydroxy-5,S-dichloronaphthalene, N49- parting solubility in water andthat correspond to thedimethylaminoethyl-2-hydroxynaphthalene-3-carboxylic formula acid amide,naphthylamine, 2-phenylaminonaphthalene, N 1 dimethylaminonaphthalene,Z-ethylaminonaphthalene,

/ indole, substituted indole wherein the sub'stituent is se- DN=NC--N=NB lected from the group consisting of methyl, phenyl,

\ methoxy, ethoxy, fi-cyanoethyl, chloro, nitro, cyano, fluoro S andbromo; pyrazole, l-phenyl-S-aminopyrazole, pyrazwherein B and D are eacha Component Selected from the olone, substituted pyrazolone wherein thesubstituent is group consisting of a C0mp0nent of the formula selectedfrom the group consisting of phenyl, C -a1kyl,

d hydroxyethyl, cyanoethyl, chlorophenyl and carbomethl i oxy;8-hydroxyquinoline, 1-methyl'4-hydroxyquino1ine-2,

N ethyl-3-hydroxy-7-methyl-1,2,3,4-tetrahydroquinoline,

Q barbituric acid, 1,3-indandione, 1,8-naphthindandione, di-

0 2 medone, aceto-acetic acid anilide, meta-hydroxy-N,N-diethylaniline,3-hydroxy-4'-methyldiphenylamine, hydroquinone-monomethyl ether,acetylacetone, S-hydroxybenzthiazole,1,2-diphenylpyrazolidine-3,S-dione, 1,2,3,4-tetrahydroquinoline,tetrahydroquinoline, N,fl-cyanoethyl, N-flyy-dihydroxypropyl-7-methoxy-tetrahydroquinoline, N-fl-'y-dihydroxypropyl-S-acetylamino-tetrahydroquinoline, N-B-hydroxyethyl-Z,2,4-trimethyl-tetrahydroquinoline,N-fihydroxyethylbenzomorpholine andN-B,'y-dihydroxypropyl-5-acetylaminobenzomorpholine; and D may be alsoor aminocarbon l; R and R are each h dro en, unsub- 'stituted alkyl ofirom l to 4 iarbon atom: or alkyl from unSubSmu.ted aryl or q subsnmtedby hydroxy,n1tro, chlorine, bromine, cyano, C -C -alkyl,

l to 4 carbon atoms substituted by phenyl, halogen, C C I alkoxy,hydroxy, cyano, cyanethoxy, C -C -hydrocar- 2 5 and g T z i i i f h f 1bylcarbamyloxy, C -C -hydrocarbylcarbonyloxy, C C yes u s as c alme m 6mm o t e hydrocarbyloxycarbonyloxy, C C hydrocarbylcarbonyld amino,chloroacetyl, triazinylamino substituted by chlod N I l rine, C -C-alkoXy or C -c -alkoxyalkoxy, hydroxyphen- RRZN N: C N:N NRXR: oxy,nitrophenoxy, carb-C -alkoxy, nitro, fl'-acetylethoxycarbonyl,(fl'-cyano)-ethoxycarbonyl, (j3'-hydroxc c y)-ethoxycarbonyl,(B-methoxy)-ethoxycarbonyl, (B'- acetoxy)-ethoxycarbonyl, carboxy,acetyl, --'NH triin which d and c are each hydrogen, halogen, loweralkyl, methylamino, diethylamino or cyanoacetoxy; and a coulower alkoxy,lower alkylmercapto, phenyl, phenylmerpling component selected from thegroup consisting of capto, phenyloxy, cyclohexyl, cyclohexylmethyl orbenzyl,

in which d and c are hydrogen, halogen, lower alkyl, lower alkoxy, loweralkylmercapto, phenyl, phenylmer- 55 capto, phenyloxy, cyclohexyl,cyclohexylmethyl or benzyl, 0 can be also C -C -acylamino, wherein theacyl is unsubstituted C C -monocarboxylic acid acyl, chlorophenoxy, C -C-alkanesulfonyl, trifiuoromethyl, benzenesulfonyl, toluenesulfonyl, C C-alkylcarbamyl, C -C 60 alkyloxycarbonyl, phenylaminocarbonyl,phenoxycarbonyl c can be also C -C -acylamino, wherein the acyl isunsubstituted C C -monocarboxylic acidacyl, chlorophenoxy, C -C-alkanesulfonyl, benzenesulfonyl, toluenesulfonyl, trifiuoromethyl, C C-alky1carbamyl, C -C -alkyloxycarbonyl, phenylaminocarbonyl,phenoxycarbonyl or aminocarbonyl; R and R are each hydrogen,unsubstituted alkyl of from 1 to 4 carbon atoms, or alkyl from 1 to 4carbon atoms substituted by phenyl, halogen, C -C alkoxy, hydroxy,cyano, cyanethoxy, C -C -hydrocarbylcarbamyloxy, C -C-hydrocarbylcarbonyloxy, C -C -hydrocarbyloxycarbonyloxy, C -Chydrocarbylcarbonylamino, chloroacetyl, triazinylamino substituted bychlorine, C -C -alkoxy or c -c -alkoxy-alkoxy, hydroxyphenoxy,nitrophenoxy, carb-C -alkoxy, nitro, ;3'-acetylethoxycarbonyl,(/3'-cyano)-ethoxy-carbonyl, 8'-hydroxy)-ethoxycarbonyl, (fi'-methoxy)-ethoxycarbonyl, (5'- References Cited UNITED STATES PATENTS 989,9534/1911 Dresse] et a1. 260-158 LEWIS GOTTS, Primary Examiner D. M.PAPUGA, Assistant Examiner US. Cl. X.R.

862, 173; 260-146 R, 153, 154, 155, 156, 239.9, 465 D, 465 E, 490, 556AR, 556 B

